Method of subatmospheric plasma-enhanced ALD using capacitively coupled electrodes with narrow gap

ABSTRACT

A method for depositing a film by plasma-enhanced subatmospheric-pressure atomic layer deposition (subatmospheric PEALD) is conducted using capacitively coupled parallel plate electrodes with a gap of 1 mm to 5 mm, wherein one cycle of subatmospheric PEALD includes: supplying a precursor in a pulse to the reaction chamber; continuously supplying a reactant to the reaction chamber; continuously supplying an inert gas to the reaction chamber; continuously controlling a pressure of the reaction chamber in a range of 15 kPa to 80 kPa; and applying RF power for glow discharge in a pulse to one of the parallel plate electrodes.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention generally relates to a method of plasma-enhanced atomic layer deposition (PEALD), particularly a method of subatmospheric PEALD using capacitively coupled electrodes with a narrow gap.

Description of the Related Art

Conventionally, in plasma-enhanced atomic layer deposition (PEALD), a plasma is generated in between two parallel plate electrodes that are spaced about 1 to 5 cm apart, from a source gas at low pressure (1 to 10 mTorr) (Stephan Heil, “Plasma-Assisted Atomic Layer Deposition of Metal Oxides and Nitrides”, Technische Universiteit Eindhoven, 2007, p. 6). Since PEALD uses a self-limiting adsorption reaction process, conformality of a thin film deposited by PEALD is high. However, as device miniaturization progresses, PEALD faces a problem that film properties such as chemical resistance and dry etching resistance of a film deposited on a sidewall of a fine trench are inferior to those of a film deposited on a flat surface due to uneven ion bombardment by a plasma where ion bombardment is weaker at the sidewall than that on the flat surface.

Any discussion of problems and solutions in relation to the related art has been included in this disclosure solely for the purposes of providing a context for the present invention, and should not be taken as an admission that any or all of the discussion was known at the time the invention was made.

SUMMARY OF THE INVENTION

In some embodiments of the present invention, thermal plasma is generated by PEALD at subatmospheric pressure using a conventional or any suitable capacitively coupled plasma (CCP) apparatus wherein process pressure is significantly increased and the gap between two parallel plate electrodes is significantly narrowed to 5 mm or less. In some embodiments, silicon-based insulation films or metal-based insulation films can effectively be deposited using subatmospheric PEALD, wherein properties of a film deposited at the sidewall of a trench or other patterned recess are remarkably improved, and, for example, surprisingly, wet etch rate (WER) of the sidewall film can be rendered approximately the same as that of top (blanket) film. In some embodiments, a carbon-based film which normally shows poor conformality due to insufficient ion bombardment at the sidewall even using an ALD mode can be deposited by subatmospheric PEALD, wherein the conformality of a deposited carbon-based film can significantly be improved.

For purposes of summarizing aspects of the invention and the advantages achieved over the related art, certain objects and advantages of the invention are described in this disclosure. Of course, it is to be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment of the invention. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught herein without necessarily achieving other objects or advantages as may be taught or suggested herein.

Further aspects, features and advantages of this invention will become apparent from the detailed description which follows.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features of this invention will now be described with reference to the drawings of preferred embodiments which are intended to illustrate and not to limit the invention. The drawings are greatly simplified for illustrative purposes and are not necessarily to scale.

FIG. 1A is a schematic representation of a PEALD (plasma-enhanced atomic layer deposition) apparatus for depositing a dielectric film usable in an embodiment of the present invention.

FIG. 1B illustrates a schematic representation of a precursor supply system using a flow-pass system (FPS) usable in an embodiment of the present invention.

FIG. 2 shows a schematic process sequence of subatmospheric PEALD in one cycle according to an embodiment of the present invention using one precursor wherein a cell in gray represents an ON state whereas a cell in white represents an OFF state, and the width of each cell does not represent duration of each process.

FIG. 3 shows a schematic process sequence of subatmospheric PEALD in one cycle according to an embodiment of the present invention using two precursors wherein a cell in gray represents an ON state whereas a cell in white represents an OFF state, and the width of each cell does not represent duration of each process.

FIG. 4 shows a schematic process sequence of subatmospheric PEALD in one cycle according to another embodiment of the present invention using two precursors wherein a cell in gray represents an ON state whereas a cell in white represents an OFF state, and the width of each cell does not represent duration of each process.

FIG. 5 shows a schematic process sequence of subatmospheric PEALD in one cycle and a schematic process sequence of subsequent subatmospheric surface treatment in one cycle according to an embodiment of the present invention wherein a cell in gray represents an ON state whereas a cell in white represents an OFF state, and the width of each cell does not represent duration of each process.

FIG. 6 shows a schematic process sequence of subatmospheric surface treatment in one cycle according to an embodiment of the present invention wherein a cell in gray represents an ON state whereas a cell in white represents an OFF state, and the width of each cell does not represent duration of each process.

FIG. 7 is a schematic representation of a subatmospheric PEALD apparatus for depositing a dielectric film usable in an embodiment of the present invention.

FIG. 8 is a flowchart illustrating a process sequence of subatmospheric PEALD according to an embodiment of the present invention.

FIG. 9 shows minimum RF power required for ignition of a plasma at pressures of 0.5 kPa and 30 kPa when varying concentration of oxygen in a reactant gas, wherein (a) shows when the reactant gas contains He, and (b) shows when the reactant gas contains Ar.

DETAILED DESCRIPTION OF EMBODIMENTS

In this disclosure, “gas” may include vaporized solid and/or liquid and may be constituted by a single gas or a mixture of gases, depending on the context. Likewise, an article “a” or “an” refers to a species or a genus including multiple species, depending on the context. In this disclosure, a process gas introduced to a reaction chamber through a showerhead may be comprised of, consist essentially of, or consist of a silicon-containing precursor and an additive gas. The additive gas includes a gas for oxidizing and/or nitriding the precursor when RF power is applied to the additive gas. The precursor and the additive gas can be introduced as a mixed gas or separately to a reaction space. The precursor can be introduced with a carrier gas such as a rare gas. A gas other than the process gas, i.e., a gas introduced without passing through the showerhead, may be used for, e.g., sealing the reaction space, which includes a seal gas such as a rare gas. In some embodiments, “film” refers to a layer continuously extending in a direction perpendicular to a thickness direction substantially without pinholes to cover an entire target or concerned surface, or simply a layer covering a target or concerned surface. In some embodiments, “layer” refers to a structure having a certain thickness formed on a surface or a synonym of film or a non-film structure. A film or layer may be constituted by a discrete single film or layer having certain characteristics or multiple films or layers, and a boundary between adjacent films or layers may or may not be clear and may be established based on physical, chemical, and/or any other characteristics, formation processes or sequence, and/or functions or purposes of the adjacent films or layers. Further, in this disclosure, any two numbers of a variable can constitute a workable range of the variable as the workable range can be determined based on routine work, and any ranges indicated may include or exclude the endpoints. Additionally, any values of variables indicated (regardless of whether they are indicated with “about” or not) may refer to precise values or approximate values and include equivalents, and may refer to average, median, representative, majority, etc. in some embodiments. Further, in this disclosure, the terms “constituted by” and “having” refer independently to “typically or broadly comprising”, “comprising”, “consisting essentially of”, or “consisting of” in some embodiments. In this disclosure, any defined meanings do not necessarily exclude ordinary and customary meanings in some embodiments.

In the present disclosure where conditions and/or structures are not specified, the skilled artisan in the art can readily provide such conditions and/or structures, in view of the present disclosure, as a matter of routine experimentation.

In all of the disclosed embodiments, any element used in an embodiment can be replaced with any elements equivalent thereto, including those explicitly, necessarily, or inherently disclosed herein, for the intended purposes. Further, the present invention can equally be applied to apparatuses and methods.

The embodiments will be explained with respect to preferred embodiments. However, the present invention is not limited to the preferred embodiments.

In an embodiment, a method for depositing a film by plasma-enhanced subatmospheric-pressure atomic layer deposition (subatmospheric PEALD), comprises: (1) placing a substrate between capacitively coupled parallel plate electrodes in an evacuatable reaction chamber, wherein a distance between the parallel plate electrodes is in a range of 1 mm to 5 mm; and (2) depositing a film having a desired thickness (e.g., 2 to 50 nm, typically 10 to 30 nm) on the substrate by plasma-enhanced atomic layer deposition (PEALD), each cycle of which comprises: (i) supplying a precursor in a pulse to the reaction chamber; (ii) continuously supplying a reactant to the reaction chamber; (iii) continuously supplying an inert gas to the reaction chamber; (iv) continuously controlling a pressure of the reaction chamber in a range of 15 kPa to 80 kPa; and (v) applying RF power for glow discharge in a pulse to one of the parallel plate electrodes, wherein the pulse of supplying the precursor and the pulse of applying RF power do not overlap.

In some embodiments including the above embodiment, the distance between the parallel plate electrodes may be defined as a distance between main planes of the respective parallel plate electrodes when having irregularities on the surfaces, an average distance between the parallel plate electrode when having concave/convex surfaces, and/or a distance between areas of the respective parallel plate electrodes when having sizes larger than a substrate, which areas are defined by an outer periphery of the substrate. The distance between the electrodes is typically in a range of 1 to 5 mm, preferably in a range of 1 to 3 mm where a thickness of a substrate is typically 0.7 mm.

In some embodiments including the above embodiment, the term “precursor” refers generally to a compound that participates in the chemical reaction that produces another compound, and particularly to a compound that constitutes a film matrix or a main skeleton of a film, whereas the term “reactant” refers to a compound that is not a precursor and activates a precursor, modifies a precursor, or catalyzes a reaction of a precursor, and the term “inert gas” refers to a gas which is not a precursor nor reactant gas and is inactive or inert when in a non-excited state, but may be active or reactive when in an excited state. In some embodiments, the inert gas is not a reactant and includes noble gases.

In the above, the term “continuously” refers to without interruption in space (e.g., uninterrupted supply over the substrate), without interruption in flow (e.g., uninterrupted inflow), and/or at a constant rate (the term need not satisfy all of the foregoing simultaneously), depending on the embodiment. In some embodiments, “continuous” flow has a constant flow rate (alternatively, even through the flow is “continuous”, its flow rate may be changed with time). In some embodiments, in a “continuous” sequence, steps are “continuously” conducted in order without an intervening step except an auxiliary step or other negligible step, e.g., valve operation, in the context. Continuous feeding of a reactant gas and an inert gas is effective in increasing purge efficiency particularly under a subatmospheric pressure. The continuous flow can be achieved using a flow-pass system (FPS) which is described later. In some embodiments, the pressure of the reaction chamber is constant throughout steps (i) to (v).

In this disclosure, the term “subatmospheric pressure” refers to a pressure lower than atmospheric pressure (about 101 kPa), typically in a range of 15 kPa to 80 kPa, preferably in a range of 15 kPa to 30 kPa. At subatmospheric pressure, glow discharge, not arc discharge, can be realized under conditions disclosed in this disclosure.

Accordingly, when the substrate has a trench pattern on which the film is deposited, properties of a film deposited on a sidewall of the trench can be as good as those of a film deposited on a flat surface, even when the trench has a high aspect ratio (e.g., 2 to 10, 3 to 5) with a width of 10 nm to 50 nm, for example.

In some embodiments, subatmospheric PEALD is conducted using a conventional or any suitable PEALD apparatus, i.e., a process of low-pressure PEALD or other treatment and a process of subatmospheric PEALD or other treatment can be conducted in combination in the same reactor while continuously operating an exhaust system using a vacuum pump. In some embodiments where a low-pressure PEALD apparatus which is operable under a process pressure of 1 to 10 mTorr, a pressure of the reaction chamber is continuously controlled in a range of 15 kPa to 80 kPa by conducting at least one (preferably at least two) of the following operations while running a vacuum pump which exhausts gases from the reaction chamber: (a) passing the exhausting gases through a throttle valve provided downstream of the reaction chamber and upstream of the vacuum pump, (b) reducing flow of the exhausting gases while passing said gases through at least one auto pressure controller (APC) provided downstream of the reaction chamber and upstream of the vacuum pump, (c) supplying ballast gas to a flow of the exhausting gases downstream of the reaction chamber and upstream of the vacuum pump, and (d) reducing rotational speed of a motor of the vacuum pump.

In some embodiments, operation (a) is conducted wherein the throttle valve is an orifice gasket. Alternatively, the throttle valve can be a needle valve. In some embodiments, operation (b) is conducted wherein two APCs are provided in series. In some embodiments, operation (c) is further conducted wherein the ballast gas is nitrogen gas which is supplied between the two APCs. In some embodiments, operation (d) is conducted wherein the rotational speed of the motor is reduced by an inverter device connected to the motor.

In some embodiments, the RF power is in a range of 0.707 W/cm² to 7.07 W/cm² (wattage per area of a substrate), preferably in a range of 1.0 W/cm² to 3.0 W/cm². In some embodiments, the RF power has a frequency of 1 kHz to 100 MHz, preferably 1 MHz to 50 MHz.

In some embodiments, the film is constituted by silicon or metal oxide, silicon or metal nitride, silicon or metal carbide, silicon or metal oxynitride, or silicon or metal carbonitride.

In some embodiments, the precursor is selected from the group consisting of H_(a)Si_(b)R_(c), R¹ _(a)Si_(b)R² _(c), H_(a)Me_(b), and R¹ _(a)Me_(b)R² _(c), wherein R, R¹, and R² are (N(C_(x)H_(y))H)_(z), (N(C_(x)H_(y))₂)_(z), (OC_(x)H_(y))_(z), halogen, OH, or non-cyclic or cyclic C_(x)H_(y) having double or triple bonds, R¹ and R² are different, and a, b, c, x, y, and z are integers. In some embodiments, the precursors include, aminosilane such as bisdimethylaminosilane and bisdiethylaminosilane, silicon halide such as dichlorotetramethyldisilane and dimethyldichlorosilane, and silicon hydrocarbon such as divinyldimethylsilane and phenylsilane, any one of which can be used singly or any two or more of which can be used in any combination. In some embodiments, in place of silicon, a metal-based precursor can be used. As for a metal, Ti, Zr, and/or Al can be used. In some embodiments, the precursor is constituted by a first precursor and a second precursor which is different from the first precursor, and the first precursor and the second precursor are alternately used when repeating the cycle of PEALD. In some embodiments, the precursor is constituted by a first precursor and a second precursor which is different from the first precursor, and step (i) comprises (ia) supplying the first precursor in a pulse to the reaction chamber, and then (ib) supplying the second precursor in a pulse to the reaction chamber. In some embodiments, three different precursors can be used.

In some embodiments, the reactant is one or more gases selected from the group consisting of oxidizing gases (such as oxygen, ozone, carbon dioxide, and/or ethanol), nitriding gases (such as ammonia, nitrogen, and/or hydrazine), and hydrogen gas.

In some embodiments, the inert gas is nitrogen gas and/or noble gas, and in some embodiments, the inert gas is solely He, Ar, or a mixture of He and Ar.

In some embodiments, the method further comprises, after one or more cycles of PEALD, conducting surface treatment comprising: (I) continuously supplying the inert gas to the reaction chamber; (II) continuously controlling the pressure of the reaction chamber in the range of 15 kPa to 80 kPa; and (III) applying RF power for glow discharge in a pulse to the one of the parallel plate electrodes, wherein no precursor is supplied during the surface treatment. In some embodiments, the surface treatment further comprises continuously supplying a reactant to the reaction chamber. For example, the surface treatment may be conducted using a gas consisting of an inert gas (excluding a reactant gas and precursor), or a combination of an inert gas and one of the reactant gas: oxygen, nitrogen, a combination of nitrogen and hydrogen (excluding a precursor). The surface treatment can further improve properties such as wet etch rate of a film which is deposited not only on a flat surface but also on a sidewall of a trench. Since the surface treatment is conducted under a subatmospheric pressure which is approximately 100 times, for example, higher than process pressure of conventional surface treatment, plasma density and radical density can be increased by approximately 100 times, thereby improving film properties in a significantly short period of time. The above subatmospheric surface treatment can be conducted not only after film formation by subatmospheric PEALD, but also after film formation by low-pressure PEALD.

In some embodiments, a method for treating a surface of a film on a substrate by plasma-enhanced subatmospheric-pressure treatment, comprises: (1) depositing the film on the substrate placed between capacitively coupled parallel plate electrodes in an evacuatable reaction chamber by plasma-enhanced atomic layer deposition (PEALD) under a pressure of less than 5 kPa, wherein a distance between the parallel plate electrodes is in a range of 1 mm to 5 mm; and (2) after one or more cycles of PEALD, continuously conducting a cycle of surface treatment comprising: (i) continuously supplying an inert gas to the reaction chamber; (ii) continuously controlling a pressure of the reaction chamber in a range of 15 kPa to 80 kPa; and (iii) applying RF power for glow discharge in a pulse to one of the parallel plate electrodes, wherein no precursor is supplied during the surface treatment.

In some embodiments, the cycle of the surface treatment further comprises continuously supplying a reactant to the reaction chamber. In some embodiments, step (ii) comprises conducting at least one of the following operations while running a vacuum pump which exhausts gases from the reaction chamber: (a) passing the exhausting gases through a throttle valve provided downstream of the reaction chamber and upstream of the vacuum pump, (b) reducing flow of the exhausting gases while passing said gases through at least one auto pressure controller (APC) provided downstream of the reaction chamber and upstream of the vacuum pump, (c) supplying ballast gas to a flow of the exhausting gases downstream of the reaction chamber and upstream of the vacuum pump, and (d) reducing rotational speed of a motor of the vacuum pump.

The embodiments will be explained with respect to the drawings. However, the present invention is not limited to the drawings.

FIG. 2 shows a schematic continuous process sequence of subatmospheric PEALD in one cycle according to an embodiment of the present invention using one precursor wherein a cell in gray represents an ON state whereas a cell in white represents an OFF state, and the width of each cell does not represent duration of each process. In the sequence illustrated in FIG. 2, the precursor is supplied in a pulse (“Feed”) using a carrier gas and a dilution gas (collectively referred to as “Inert gas”) which are continuously supplied. This can be accomplished using a flow-pass system (FPS) wherein a carrier gas line is provided with a detour line having a precursor reservoir (bottle), and the main line and the detour line are switched, wherein when only a carrier gas is intended to be fed to a reaction chamber, the detour line is closed, whereas when both the carrier gas and a precursor gas are intended to be fed to the reaction chamber, the main line is closed and the carrier gas flows through the detour line and flows out from the bottle together with the precursor gas. In this way, the carrier gas can continuously flow into the reaction chamber, and can carry the precursor gas in pulses by switching the main line and the detour line. FIG. 1B illustrates a precursor supply system using a flow-pass system (FPS) according to an embodiment of the present invention (black valves indicate that the valves are closed). As shown in (a) in FIG. 1B, when feeding a precursor to a reaction chamber (not shown), first, a carrier gas such as Ar (or He) flows through a gas line with valves b and c, and then enters a bottle (reservoir) 20. The carrier gas flows out from the bottle 20 while carrying a precursor gas in an amount corresponding to a vapor pressure inside the bottle 20, and flows through a gas line with valves f and e, and is then fed to the reaction chamber together with the precursor. In the above, valves a and d are closed. When feeding only the carrier gas (noble gas) to the reaction chamber, as shown in (b) in FIG. 1B, the carrier gas flows through the gas line with the valve a while bypassing the bottle 20. In the above, valves b, c, d, e, and f are closed.

Under subatmospheric pressure, efficiency of purging is significantly low. However, the FPS can compensate for the insufficient purging under subatmospheric pressure. Further, extremely high flow rate of a dilution gas such as 10 slm to 60 slm (typically 20 slm to 50 slm) improves efficiency of purging.

In FIG. 2, the precursor is provided with the aid of a carrier gas (“Inert gas”). Since ALD is a self-limiting adsorption reaction process, the number of deposited precursor molecules is determined by the number of reactive surface sites and is independent of the precursor exposure after saturation, and a supply of the precursor is such that the reactive surface sites are saturated thereby per cycle. A plasma for deposition is generated by applying RF power (“RF”) in a pulse (“RF”) in situ in a reactant gas (“Reactant”) (e.g., an ammonia gas) that flows continuously throughout the deposition cycle, while the inert gas is also continuously fed to the reaction space, without feeding the precursor, thereby forming a monolayer.

As mentioned above, each pulse or phase of each deposition cycle is preferably self-limiting. An excess of reactants is supplied in each phase to saturate the susceptible structure surfaces. Surface saturation ensures reactant occupation of all available reactive sites (subject, for example, to physical size or “steric hindrance” restraints) and thus ensures excellent step coverage. In some embodiments the pulse time of one or more of the reactants can be reduced such that complete saturation is not achieved and less than a monolayer is adsorbed on the substrate surface. After “Feed”, the reaction space is purged (“Purge 1”) where no precursor is fed to the reaction space, while the inert gas and reactant gas are continuously fed to the reaction space, without applying RF power, thereby removing non-chemisorbed precursor and excess gas from the surface of the substrate. After “RF”, the reaction space is purged (“Purge 2”) where the inert gas and reactant gas are continuously fed to the reaction space, without feeding the precursor and without applying RF power to the reaction space, thereby removing by-products and excess gas from the surface of the substrate. Due to the continuous flow of the reactant gas, and also due to the continuous flow of the inert gas entering into the reaction space as a constant stream into which the precursor is injected intermittently or in pulses, purging can be conducted efficiently to remove excess gas and by-products quickly from the surface of the layer, thereby efficiently continuing multiple PEALD cycles.

Throughout each cycle, the reaction space is controlled at subatmospheric pressure (“Pressure”). The pressure control can be conducted as follows, for example, so that subatmospheric PEALD can be performed using a low-pressure PEALD apparatus while continuously running a vacuum pump or an exhaust system.

FIG. 7 is a schematic representation of a subatmospheric PEALD apparatus for depositing a dielectric film usable in an embodiment of the present invention. Subatmospheric PEALD is conducted in a reactor 31. The pressure in a reaction chamber 31 is detected and monitored continuously or intermittently, and a controller 40 controls the process pressure according to a flowchart or algorithm illustrated in FIG. 8, for example (which is explained below). The process pressure can be controlled by any one or more of the following operations: Operation (a) is passing exhausting gases through a throttle valve 34 provided downstream of the reaction chamber 31 and upstream of a vacuum pump 32. When passing the exhausting gases through the throttle valve 34 provided in a pipe c, a valve 35 (e.g., a gate valve, rather than an on-off valve, since pipes b and c have an inner diameter of 1.375″ and an outer diameter of 2.16″, for example) is closed. The throttle valve may be an orifice gasket. The pipe a which bypasses the pipe b is, for example, a ¼″ pipe which is smaller than the pipe b so as to create more pressure loss to reduce vacuum force (the degree of vacuum) by the vacuum pump 32. The orifice gasket 34 has, for example, an opening having a diameter of about 0.5 mm. The throttle valve can be a needle valve which is an opening-adjustable valve.

Operation (b) is reducing flow of the exhausting gases while passing said gases through at least one auto pressure controller (APC) 37, 38 provided in the pipe c downstream of the reaction chamber 31 and upstream of the vacuum pump 32. By using the APC 37, 38, the vacuum force (the degree of vacuum) by the vacuum pump 32 can effectively be reduced.

Operation (c) is supplying ballast gas through a pipe d from a ballast gas source 33 to a flow of the exhausting gases downstream of the reaction chamber 31 and upstream of the vacuum pump 32. A valve 36 provided in the pipe d is, for example, an air-operated valve which controls a ballast gas flow. In this configuration, the pipe d is connected to the pipe c between the APC 37 and the APC 38, so that the APC 37 functions as a check valve which prevents a backflow of the ballast gas. The ballast gas is, for example, nitrogen gas, and a flow rate is about 10 L/min to about 100 L/min, typically about 10 L/min to about 30 L/min. By using the ballast gas, the vacuum force (the degree of vacuum) by the vacuum pump 32 can effectively be reduced.

Operation (d) is reducing rotational speed of a motor of the vacuum pump 32. Operation (d) is conducted wherein the rotational speed of the motor is reduced by an inverter device 39 connected to the motor. By using the inverter device 39 which changes a frequency of current to adjust the rotation speed of the motor, the vacuum pump having an exhaust capacity of, for example, about 6,000 L/min can be reduced to about 2,000 L/min.

FIG. 8 is a flowchart illustrating a process sequence of subatmospheric PEALD according to an embodiment of the present invention. The controller 40 stores a program to execute the algorithm. In step 1, the pressure of the reaction chamber 31 is detected and monitored. In step 2, the measured pressure is compared with a preset target pressure, and it is determined if the measured pressure is lower than the set value of the target pressure. If the measured pressure is lower than the set value, in step 3, one or more of operations (a) to (d) which have been selected are conducted while running the vacuum pump 32. In step 4 when this step (operation (a)) is preselected, the controller 40 controls the exhausting gases to pass through the orifice gasket 34 while closing the valve 35. In step 5 when this step (operation (b)) is preselected, the controller 40 controls the APCs 37 and 38 to reduce flow of the exhausting gases. In step 6 when this step (operation (c)) is preselected, the controller 40 opens the valve 36 to supply the ballast in the pipe c between the APCs 37 and 38. In step 7 when this step (operation (d)) is preselected, the controller 40 reduces the rotation speed of the motor of the vacuum pump 32.

In some embodiments, the pressure in the reaction chamber is controlled continuously at a substantially constant value using the flow-pass system (FPS) illustrated in FIG. 1B, for example, so that plasma stability can be improved, and also throughput can be improved by eliminating a time period for stabilizing gas flows. The term “substantially” constant or the like may refer to an immaterial fluctuation, a fluctuation that does not materially affect the target or intended properties, or a fluctuation recognized by a skilled artisan as nearly zero, such as less than 10%, less than 5%, or any ranges thereof relative to the total or the referenced value in some embodiments.

A skilled artisan will appreciate that the apparatus includes one or more controller(s) (not shown) programmed or otherwise configured to cause the deposition and reactor cleaning processes described elsewhere herein to be conducted. The controller(s) are communicated with the various power sources, heating systems, pumps, robotics, and gas flow controllers or valves of the reactor, as will be appreciated by the skilled artisan.

The process cycle can be performed using any suitable apparatus including an apparatus illustrated in FIG. 1A, for example. FIG. 1A is a schematic view of a PEALD apparatus, desirably in conjunction with controls programmed to conduct the sequences described below, usable in some embodiments of the present invention. In this figure, by providing a pair of electrically conductive flat-plate electrodes 4, 2 in parallel and facing each other in the interior 11 (reaction zone) of a reaction chamber 3, applying HRF power (13.56 MHz or 27 MHz) 25 to one side, and electrically grounding the other side 12, a plasma is excited between the electrodes. A temperature regulator is provided in a lower stage 2 (the lower electrode), and a temperature of a substrate 1 placed thereon is kept constant at a given temperature. The upper electrode 4 serves as a shower plate as well, and reactant gas (and noble gas) and precursor gas are introduced into the reaction chamber 3 through a gas line 21 and a gas line 22, respectively, and through the shower plate 4. Additionally, in the reaction chamber 3, a circular duct 13 with an exhaust line 7 is provided, through which gas in the interior 11 of the reaction chamber 3 is exhausted. Additionally, a transfer chamber 5 disposed below the reaction chamber 3 is provided with a seal gas line 24 to introduce seal gas into the interior 11 of the reaction chamber 3 via the interior 16 (transfer zone) of the transfer chamber 5 wherein a separation plate 14 for separating the reaction zone and the transfer zone is provided (a gate valve through which a wafer is transferred into or from the transfer chamber 5 is omitted from this figure). The transfer chamber is also provided with an exhaust line 6. In some embodiments, the deposition of multi-element film and surface treatment are performed in the same reaction space, so that all the steps can continuously be conducted without exposing the substrate to air or other oxygen-containing atmosphere. In some embodiments, a remote plasma unit can be used for exciting a gas.

In the apparatus illustrated in FIG. 1A, in order to increase an inert gas flow flowing into the reaction chamber, an inert gas may also be introduced into the reaction chamber through a side flow line 17, in addition to the gas flow from the showerhead 4. Alternatively, in place of the showerhead, only the side flow line is used to introduce the process gases, wherein an upper electrode without a shower plate can replace the showerhead.

In some embodiments, in the apparatus depicted in FIG. 1A, the system of switching flow of an inactive gas and flow of a precursor gas illustrated in FIG. 1B (described earlier) can be used to introduce the precursor gas in pulses without substantially fluctuating pressure of the reaction chamber.

In some embodiments, a dual chamber reactor (two sections or compartments for processing wafers disposed closely to each other) can be used, wherein a reactant gas and a noble gas can be supplied through a shared line whereas a precursor gas is supplied through unshared lines.

In some embodiments, the subatmospheric PEALD cycles may be conducted under the conditions shown in Table 1 below.

TABLE 1 (numbers are approximate) Conditions for subatmospheric PEALD Substrate temperature 50 to 550° C. (preferably 100 to 400° C.) Electrode gap (a thickness of 1.0 to 5.0 mm (preferably 1.0 to 3.0 mm) a substrate is about 0.7 mm) Pressure 15 to 80 kPa (preferably 15 to 50 kPa) Flow rate of reactant gas 100 to 3000 sccm (preferably 200 to (continuous) 2000 sccm) Flow rate of carrier gas 500 to 5000 sccm (preferably 1000 to (continuous) 2000 sccm) Flow rate of dilution gas 0.1 to 3 slm (preferably 0.2 to 2 slm) (continuous) Flow rate of precursor Corresponding to the flow rate of carrier gas RF power (13.56 MHz) 500 to 5000 W (preferably 1000 to for a 300-mm wafer 2000 W) Duration of “Feed” 0.1 to 5 sec. (preferably 0.1 to 1 sec.) Duration of “Purge 1” 0.1 to 5 sec. (preferably 0.3 to 1 sec.) Duration of “RF” 0.1 to 10 sec. (preferably 0.5 to 5 sec.) Duration of “Purge 2” 0.1 to 1 sec. (preferably 0.1 to 0.5 sec.) Duration of one cycle 0.4 to 22 sec. (preferably 1 to 12 sec.) Glow rate per cycle (nm/min) 0.1 to 2 (preferably 0.3 to 1) on top surface

The above indicated RF power for a 300-mm wafer can be converted to W/cm² (wattage per unit area of a wafer) which can apply to a wafer having a different diameter such as 200 mm or 450 mm.

Typically, the thickness of the dielectric film to be etched is in a range of about 50 nm to about 500 nm (a desired film thickness can be selected as deemed appropriate according to the application and purpose of film, etc.). The dielectric film may be used for double-patterning.

In some embodiments, the process sequence may be set as illustrated in FIG. 3. FIG. 3 shows a schematic continuous process sequence of subatmospheric PEALD in one cycle according to an embodiment of the present invention using two precursors wherein a cell in gray represents an ON state whereas a cell in white represents an OFF state, and the width of each cell does not represent duration of each process.

In this embodiment, one cycle of subatmospheric PEALD comprises “Feed 1” where a 1^(st) precursor gas (“1^(st) Precursor”) is fed to a reaction space via a carrier gas (“Inert gas”) which carries the precursor without applying RF power to the reaction space, and also, a dilution gas (together with the carrier gas collectively referred to as “Inert gas”) and a reactant gas (“Reactant”) are fed to the reaction space, thereby chemisorbing the precursor gas onto a surface of a substrate via self-limiting adsorption, while continuously controlling the process pressure at a subatmospheric pressure; “Purge 1” where no precursor is fed to the reaction space, while the carrier gas, dilution gas, and reactant gas are continuously fed to the reaction space, without applying RF power, thereby removing non-chemisorbed precursor gas and excess gas from the surface of the substrate while continuously controlling the process pressure; “RF 1” where RF power is applied to the reaction space while the carrier gas, dilution gas, and reactant gas are continuously fed to the reaction space, without feeding the precursor, thereby depositing a dielectric layer through plasma surface reaction with the reactant gas in an excited state while continuously controlling the process pressure; and “Purge 2” where the carrier gas, dilution gas, and reactant gas are continuously fed to the reaction space, without feeding the precursor and without applying RF power to the reaction space, thereby removing by-products and excess gas from the surface of the substrate while continuously controlling the process pressure. In the above, “Feed 1”, “Purge 1”, “RF 1”, and “Purge 2” substantially correspond to “Feed”, “Purge 1”, “RF”, and “Purge 2” illustrated in FIG. 2, respectively. The one cycle of subatmospheric PEALD further comprises similar processes for a 2^(nd) precursor (“2^(nd) Precursor”), which comprises “Feed 2”, “Purge 3”, “RF 2”, and “Purge 4”, which substantially correspond to “Feed 1”, “Purge 1”, “RF 1”, and “Purge 2”, respectively. Due to the continuous flow of the carrier gas entering into the reaction space as a constant stream into which the precursor is injected intermittently or in pulses, and due to continuous flow of the dilution gas and reactant gas entering into the reaction space as a constant stream, the purging can be conducted efficiently to remove excess gas and by-products quickly from the surface of the layer, thereby efficiently continuing multiple ALD cycles even under subatmospheric pressure.

FIG. 4 shows a schematic continuous process sequence of subatmospheric PEALD in one cycle according to another embodiment of the present invention using two precursors wherein a cell in gray represents an ON state whereas a cell in white represents an OFF state, and the width of each cell does not represent duration of each process. In this sequence, “Feed 1”, “Purge 1”, “RF”, and “Purge 3” substantially correspond to “Feed”, “Purge 1”, “RF”, and “Purge 2” illustrated in FIG. 2, respectively. In addition, the sequence further comprises “Feed 2” and “Purge 2” for a 2^(nd) precursor (“2^(nd) Precursor”) which are inserted between “Purge 1” and “RF”.

FIG. 6 shows a schematic continuous process sequence of subatmospheric surface treatment in one cycle according to an embodiment of the present invention wherein a cell in gray represents an ON state whereas a cell in white represents an OFF state, and the width of each cell does not represent duration of each process. The subatmospheric surface treatment can be conducted after deposition of a film by the subatmospheric PEALD or low-pressure PEALD. The subatmospheric surface treatment can further improve properties of a film not only deposited on a flat surface but also deposited at a sidewall of a trench due to high plasma density under subatmospheric pressure. In FIG. 6, the sequence comprises: “Gas charge” where an inert gas (“Inert gas”) is continuously fed to the reaction space while continuously controlling the pressure (“Pressure”) at a subatmospheric pressure as discussed in this disclosure, without applying RF power to the reaction chamber and without feeding a precursor or a reactant gas (alternatively, in another embodiment, a reactant gas may be fed); “Stabilize” where process conditions are maintained until gas flow is stabilized; “RF” where RF power is applied to the reaction space; and “Purge” where the reaction space is purged.

In some embodiments, subatmospheric surface treatment may be conducted under conditions shown in Table 2 below.

TABLE 2 (numbers are approximate) Conditions for subatmospheric surface treatment Substrate temperature Same as in 1 to 5 subatmospheric PEALD Pressure Same as in subatmospheric PEALD Inert gas Same as in subatmospheric PEALD Flow rate of inert gas Same as in subatmospheric PEALD (continuous) RF power (13.56 MHz) for 100 to 5000 W (preferably 300 to 3000 W) a 300-mm wafer Duration of “Gas change” 1 to 15 sec. (preferably sec.) Duration of “Stabilize” 2 to 15 sec. (preferably 2 to 10 sec.) Duration of “RF” 0.1 to 10 sec. (preferably 0.3 to 5 sec.) Duration of “Purge” 0.1 to 2 sec. (preferably 0.1 to 1 sec.)

The above indicated RF power for a 300-mm wafer can be converted to W/cm² (wattage per unit area of a wafer) which can apply to a wafer having a different diameter such as 200 mm or 450 mm.

FIG. 5 shows a schematic continuous process sequence of subatmospheric PEALD in one cycle and a schematic process sequence of subsequent subatmospheric treatment in one cycle according to an embodiment of the present invention wherein a cell in gray represents an ON state whereas a cell in white represents an OFF state, and the width of each cell does not represent duration of each process. In this sequence, the subatmospheric PEALD comprises “Feed”, “Purge 1”, “RF”, and “Purge 2” which substantially correspond to those illustrated in FIG. 2, respectively. After repeating the above cycle m times (m is an integer of 1 to 1000, preferably 50 to 200), the subatmospheric surface treatment is initiated, which comprises “Gas charge”, “Stabilize”, “RF”, and “Purge 3” which substantially correspond to “Gas charge”, “Stabilize”, “RF”, and “Purge” illustrated in FIG. 6, respectively. The above cycle can be repeated n times (n is an integer of 1 to 1000, preferably 1 to 50). A ratio of n/m may be in a range of 1/1000 to 1/1, preferably 1/500 to 1/2.

The present invention is further explained with reference to working examples below. However, the examples are not intended to limit the present invention. In the examples where conditions and/or structures are not specified, the skilled artisan in the art can readily provide such conditions and/or structures, in view of the present disclosure, as a matter of routine experimentation. Also, the numbers applied in the specific examples can be modified by a range of at least ±50% in some embodiments, and the numbers are approximate.

EXAMPLES Examples 1 to 7

A film was formed on a Si substrate (having a diameter of 300 mm and a thickness of 0.7 mm) having trenches with an aspect ratio of 4 (a width of 25 nm, and a depth of 100 nm) by subatmospheric PEALD using a sequence illustrated in FIG. 2, one cycle of which was conducted under the common conditions shown in Table 3 (process cycle) below using the PEALD apparatus illustrated in FIG. 1A and a gas supply system (FPS) illustrated in FIG. 1B with the specific conditions and sequence indicated in Table 4.

TABLE 3 (numbers are approximate) Common Conditions for Process Cycle Carrier gas and dilution gas Ar Flow rate of carrier gas (continuous) 2 slm Precursor pulse 1 sec Purge after precursor feed pulse 2 sec RF power pulse 1 sec Purge after RF power pulse 1 sec

TABLE 4 (numbers are approximate) Dilu- Temp. Pressure RF Gap Reactant/ tion Precursor (° C.) (kPa) (W) (mm) slm (slm) *1 Bisdimethyl- 300 0.4 100 12 O₂/0.1 1 aminosilane *2 Dichlorotetra- 400 0.4 200 12 NH₃/2 1 mehyldisilane *3 Divinyldimethyl- 300 0.4 100 12 CO₂/0.1 1 silane  4 Bisdimethyl- 300 50 1,000 5 O₂/0.1 30 aminosilane  5 Bisdimethyl- 300 50 1,000 2 O₂/0.1 30 aminosilane  6 Dichlorotetra- 400 30 2,000 2 NH₃/2 50 mehyldisilane  7 Divinyldimethyl- 300 50 1,000 2 CO₂/0.1 30 silane

In Table 4, the Example numbers with “*” indicate comparative examples. Each obtained film was evaluated. Table 5 shows the results of evaluation.

TABLE 5 (numbers are approximate) Sidewall 100:1 DHF Coverage @ 100:1 DHF GPC Top WER AR4 Side WER Side/Top (nm/cycle) RI (nm/min) (%) (nm/min) WER Film *1 0.1 1.47 3.8 95 4.8 1.3 SiO *2 0.05 1.88 1.2 95 4.8 4 SiN *3 0.03 1.71 0.1 60 0.5 5 SiCO  4 0.11 1.45 3.2 95 3.8 1.2 SiO  5 0.11 1.46 2.9 105 3.0 1.0 SiO  6 0.05 1.96 0.8 97 0.9 1.1 SiN  7 0.04 1.78 0.1 89 0.1 1.0 SiCO

In Table 4, “GPC” represents growth rate per cycle, “Sidewall Coverage@AR4” represents a percentage of thickness of film deposited on a sidewall relative to thickness of film deposited on a blanket surface at a trench having an aspect ratio of 3, “RI” represents refractive index, and “100:1 DHF Top/Side WER” represents wet etch rate of a top film/side film using a solution of 100:1 DHF (diluted hydrogen fluoride).

As shown in Table 5, according to the subatmospheric PEALD disclosed herein, the target films could be deposited as if the films were deposited by low-pressure PEALD. Further, the films deposited by the subatmospheric PEALD had excellent conformality (typically about 90% or higher) and excellent uniformity of film properties (typically a ratio of side/top WER of 1.2 or less) in the trench, regardless of the type of film (Examples 4 to 7). Particularly when depositing the films constituted by SiN or SiCO where low plasma density at the sidewall was a problem in the low-pressure PEALD, resulting in uneven properties of the films deposited at the sidewall and the top surface (Examples 2 and 3), by the subatmospheric PEALD, films with excellent uniformity were deposited (Examples 6 and 7). Further, in the subatmospheric PEALD, when the gap between the electrodes was as small as about 2 mm (Example 5), even higher uniformity of film properties was achieved as compared with when the gap was about 5 mm (Example 4).

Reference Examples

In reference examples, ignition of a plasma under subatmospheric pressure was investigated under the conditions used in Example 5 above except for the inert gas (dilution gas), the inert gas flow rate, the oxygen flow rate, and the process pressure. The results are shown in FIG. 9. FIG. 9 shows minimum RF power required for ignition of a plasma at pressures of 0.5 kPa and 30 kPa when varying concentration of oxygen in a reactant gas, wherein (a) shows when the reactant gas contains He, and (b) shows when the reactant gas contains Ar. As shown in FIG. 9, when He was used as the inert gas as compared with Ar, a plasma was ignited more stably at a lower RF power wherein when the oxygen concentration was 4% and 7% (typically 1% or more but less than 10%), a plasma was stably ignited by an RF power of 500 W even under subatmospheric pressure, and when the oxygen concentration was 10%, a plasma was stably ignited by an RF power of 1,000 W. However, when the oxygen concentration was 0% (typically 1% or less), both He and Ar could ignite a plasma at an RF power of 500 W. Thus, when a high oxygen concentration (typically 1% or higher) is required in subatmospheric PEALD, by using He as the inert gas, a plasma can be stably ignited.

It will be understood by those of skill in the art that numerous and various modifications can be made without departing from the spirit of the present invention. Therefore, it should be clearly understood that the forms of the present invention are illustrative only and are not intended to limit the scope of the present invention. 

We claim:
 1. A method for depositing a film by plasma-enhanced subatmospheric-pressure atomic layer deposition, comprising: placing a substrate between capacitively coupled parallel plate electrodes in an evacuatable reaction chamber which is a single wafer chamber, wherein a distance between the parallel plate electrodes is in a range of 1 mm to 5 mm; and depositing a film having a desired thickness on the substrate by plasma-enhanced atomic layer deposition (PEALD), each cycle of which comprises: (i) supplying a precursor in a pulse to the reaction chamber; (ii) continuously supplying a reactant to the reaction chamber; (iii) continuously supplying an inert gas to the reaction chamber; (iv) continuously controlling a pressure of the reaction chamber in a range of 15 kPa to 80 kPa; and (v) applying RF power for glow discharge in a pulse to one of the parallel plate electrodes, wherein the pulse of supplying the precursor and the pulse of applying RF power do not overlap, wherein step (iv) comprises conducting at least two of the following operations while running a vacuum pump which exhausts gases from the reaction chamber: (a) passing the exhausting gases through a throttle valve provided downstream of the reaction chamber and upstream of the vacuum pump, (b) reducing flow of the exhausting gases while passing said gases through at least one auto pressure controller (APC) provided downstream of the reaction chamber and upstream of the vacuum pump, (c) supplying ballast gas to a flow of the exhausting gases downstream of the reaction chamber and upstream of the vacuum pump, and (d) reducing rotational speed of a motor of the vacuum pump.
 2. The method according to claim 1, wherein operation (a) is conducted wherein the throttle valve is an orifice gasket.
 3. The method according to claim 1, wherein operation (b) is conducted wherein two APCs are provided in series.
 4. The method according to claim 3, wherein operation (c) is further conducted wherein the ballast gas is nitrogen gas which is supplied between the two APCs.
 5. The method according to claim 1, wherein operation (d) is conducted wherein the rotational speed of the motor is reduced by an inverter device connected to the motor.
 6. The method according to claim 1, wherein the RF power is in a range of 0.707 W/cm² to 7.07 W/cm².
 7. The method according to claim 1, wherein the pressure of the reaction chamber is constant throughout steps (i) to (v).
 8. The method according to claim 1, wherein the substrate has a trench pattern on which the film is deposited.
 9. The method according to claim 1, wherein the film is constituted by silicon or metal oxide, silicon or metal nitride, silicon or metal carbide, silicon or metal oxynitride, or silicon or metal carbonitride.
 10. The method according to claim 1, wherein the precursor is selected from the group consisting of H_(a)Si_(b)R_(c), R¹ _(a)Si_(b)R² _(c), H_(a)Me_(b), and R¹ _(a)Me_(b)R² _(c), wherein R, R¹, and R² are (N(C_(x)H_(y))H)_(z), (N(C_(x)H_(y))₂)_(z), (OC_(x)H_(y))_(z), halogen, OH, or non-cyclic or cyclic C_(x)H_(y) having double or triple bonds, R¹ and R² are different, and a, b, c, x, y, and z are integers.
 11. The method according to claim 1, wherein the precursor is constituted by a first precursor and a second precursor which is different from the first precursor, and the first precursor and the second precursor are alternately used when repeating the cycle of PEALD.
 12. The method according to claim 1, wherein the precursor is constituted by a first precursor and a second precursor which is different from the first precursor, and step (i) comprises (ia) supplying the first precursor in a pulse to the reaction chamber, and then (ib) supplying the second precursor in a pulse to the reaction chamber.
 13. The method according to claim 1, wherein the reactant is one or more gases selected from the group consisting of oxidizing gases, nitriding gases, and hydrogen gas.
 14. The method according to claim 1, wherein the inert gas is solely He, Ar, or a mixture of He and Ar.
 15. The method according to claim 1, further comprising, after one or more cycles of PEALD, conducting surface treatment comprising: continuously supplying the inert gas to the reaction chamber; continuously controlling the pressure of the reaction chamber in the range of 15 kPa to 80 kPa; and applying RF power for glow discharge in a pulse to the one of the parallel plate electrodes, wherein no precursor is supplied during the surface treatment.
 16. The method according to claim 15, wherein the surface treatment further comprises continuously supplying a reactant to the reaction chamber.
 17. A method for treating a surface of a film on a substrate by plasma-enhanced subatmospheric-pressure treatment, comprising: depositing the film on the substrate according to claim 1; and after one or more cycles of PEALD, continuously conducting a cycle of surface treatment comprising: (vi) continuously supplying the inert gas to the reaction chamber; (vii) continuously controlling a pressure of the reaction chamber in a range of 15 kPa to 80 kPa; and (viii) applying RF power for glow discharge in a pulse to one of the parallel plate electrodes, wherein no precursor is supplied during the surface treatment.
 18. The method according to claim 17, wherein the cycle of the surface treatment further comprises continuously supplying the reactant to the reaction chamber.
 19. The method according to claim 17, wherein step (vii) comprises conducting at least one of the following operations while running the vacuum pump which exhausts gases from the reaction chamber: (a) passing the exhausting gases through the throttle valve provided downstream of the reaction chamber and upstream of the vacuum pump, (b) reducing flow of the exhausting gases while passing said gases through the at least one auto pressure controller (APC) provided downstream of the reaction chamber and upstream of the vacuum pump, (c) supplying the ballast gas to a flow of the exhausting gases downstream of the reaction chamber and upstream of the vacuum pump, and (d) reducing the rotational speed of the motor of the vacuum pump. 